Cp*(Me3P)Ir(CH3)(OTf) is known to activate C-H bonds of unactivated substrates, including methane, under remarkably mild conditions. However, there are few instances of further functionalization of the Ir-bound hydrocarbyl following the oxidative addition and subsequent reductive elimination of methane in this system. Various group transfer reactions have been successful in the field of Cp*Ir(III) C-H activation/functionalization of reactants with directing groups, hence it appeared to be possible to apply similar methods to the aforementioned complexes. Here, we report that treatment of Cp*(Me3P)Ir(CH3)(OTf) with the Wittig reagent, H2CPPh3, yields products [Cp*(Me3P)Ir(H)(η2-CH2CH2)][OTf] as well as [Cp*(Me3P)(Ph3P)Ir(CH2CH3)][OTf], and submission of Cp*(Me3P)Ir(Ph)(OTf) to the same conditions furnishes the benzyl complex [Cp*(Me3P)(Ph3P)Ir(CH2Ph)][OTf]. Further experiments and calculations suggest a methylene transfer reaction mechanism proceeding via a transient Ir(III)=CH2 intermediate.

From methane to ethylene: Investigation of methylene transfer and C–C bond formation on an iridium centre

Macromolecular Chemistry: The Second Century

[Author Benefits](https://scimeetings.acs.org/?utm_source=pubs_content_marketing&utm_medium=website&utm_campaign=0320_MCF_NPI_Launch_Spring_Homepage&ref=pubs_content_marketing)

[How to use SciMeetings](https://storage.googleapis.com/dl.morressier.com/acs/SciMeetings-ACSSpring2020-HowToGuide_M3020-Final.pdf)

[Frequently Asked Questions](https://storage.googleapis.com/dl.morressier.com/acs/SciMtng_ACSNMSp2020_FAQ_M3120_Final.pdf)

ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.